Colorant compounds, phase change ink compositions, and methods of printing

ABSTRACT

The invention encompasses a compound having the formula:                    
     wherein at least one Q 1 , Q 2 , Q 3  and Q 4  is a halogen atom and any of Q 1 , Q 2 , Q 3  and Q 4  which is not a halogen atom is a hydrogen atom; and wherein R comprises at least two carbon atoms. The invention further encompasses inclusion of such compound into phase change ink carrier compositions, as well as printing methods utilizing such compound.

BACKGROUND

1. Field of the Invention

The invention relates to new compositions of matter which can beutilized as colorant compounds. In particular applications, theinvention pertains to phase change ink formulations. In other particularapplications, the invention pertains to methods of printing.

2. Description of Relevant Art

The present invention encompasses new colorant compounds and methodologyfor incorporating such compounds into phase change inks. Phase changeinks are compositions which are in a solid phase at ambient temperature,but which exist in a liquid phase at an elevated operating temperatureof an ink jet printing device. At the jet operating temperature,droplets of liquid ink are ejected from the printing device. When theink droplets contact the surface of a printing media, they solidify toform a printed pattern. Phase change ink methodology is describedgenerally in U.S. Pat. Nos. 4,889,560; 5,372,852 and 5,827,918.

Phase change inks generally comprise a waxy organic compound (typicallya tetra-amide material), a tackifier, and a viscosity modifying agent asprimary components. An exemplary viscosity modifying agent isstearylstearamide, which can be provided to a concentration of less thanor equal to about 60% (by weight). An exemplary tackifier is KE-100Resin, an ester of tetrahydroabietic acid and glycerol, which isavailable from Arakawa Chemical Industries Ltd. Tackifiers are typicallyprovided to a concentration of less than or equal to about 30% (byweight). Exemplary tetra-amide compounds can be formed by reactingethylene diamine with a dimer acid and an appropriate fatty acid.

In addition to the above-described primary components, phase change inkscan comprise a number of secondary components, such as, for example,colorants (for example, dyes), plasticizers, and antioxidants, asdescribed in, for example, U.S. Pat. Nos. 4,889,560 and 5,372,852.

A definition which will be adopted in this disclosure and the claimsthat follow will be to refer to a phase change ink composition ascomprising a colorant and a carrier. The term “carrier” is to beunderstood to comprise everything in the phase change ink compositionbesides the colorant. In phase change ink compositions comprising morethan one colorant, the carrier will include everything except aparticular colorant of interest, and can, therefore, comprise colorantsother than that which is of interest.

A difficulty associated with phase change inks can be in solubilizingcolorants. The colorants generally comprise polar functional groups, andaccordingly are insoluble in an organic carrier of a phase change inkcomposition. Accordingly, it is desirable to develop new colorantshaving improved solubility in phase change ink carrier compositions.

An exemplary prior art colorant compound is C.I. Solvent Red 172, whichis shown below as formula 1.

Such colorant manifests a magenta color that could be useful in phasechange inks. However, C.I. Solvent Red 172 has less than satisfactorysolubility in present phase change ink carrier compositions.Accordingly, it would be desirable to form a composition havingchromophoric properties similar to C.I. Solvent Red 172, but withimproved solubility in phase change ink carrier compositions.

SUMMARY

In one aspect, the invention encompasses compounds having the formula 2:

wherein at least one Q₁, Q₂, Q₃ and Q₄ is a halogen atom and any of Q₁,Q₂, Q₃ and Q₄ which is not a halogen atom is a hydrogen atom; andwherein R comprises at least two carbon atoms. The invention furtherencompasses inclusion of such compounds into phase change ink carriercompositions, as well as printing methods utilizing such compounds.

In another aspect, the invention encompasses compounds having theformula 3:

wherein X and Y are halogen atoms and can be the same or different thanone another, and wherein R comprises at least two carbon atoms. Theinvention further comprises inclusion of such compounds in phase changeink compositions, and printing methods utilizing such compounds.

In yet another aspect, the invention encompasses compounds having theformula 4:

wherein X is a halogen atom, and wherein R comprises at least two carbonatoms. The invention further encompasses inclusion of such compoundsinto phase change ink carrier compositions, as well as printing methodsutilizing such compounds.

BRIEF DESCRIPTION OF THE DRAWING

The FIG. shows a generalized reaction scheme for forming a compoundencompassed by the present invention.

DETAILED DESCRIPTION

Colorants encompassed by embodiments of the present invention arerepresented generally as compounds having a formula 2:

where at least one of Q₁, Q₂, Q₃ and Q₄ is a halogen atom and any of Q₁,Q₂, Q₃ and Q₄ which is not a halogen atom, is a hydrogen atom. The Rgroup of compounds having formula 2 comprises at least two carbon atoms.

Advantageously, a colorant encompassed by general formula 2 is morespecifically described as compounds having formula 3:

Such colorant comprises an aromatic hexagonal ring (shown as a hexagonalring with a circle in the middle) bonded to a nitrogen, which in turn isbonded to a 3-ring structure (specifically, an anthraquinonederivative). Compounds of formula 3 further comprise a carbon-containinggroup R which is bonded to the aromatic hexagonal ring in a paraposition relative to the nitrogen atom. Such R groups comprise at leasttwo carbon atoms and in some embodiments comprise from 2 to about 100carbon atoms. In some advantageous embodiments compounds of formula 3comprise from 2 to about 50 carbon atoms, and in some embodimentscomprise from about 4 to about 20 carbon atoms. Further, the R group ofcompounds of formula 3 are generally an aliphatic chain, and accordinglycan comprise (CH₂)_(n),(CH₃) wherein n is an integer of from 1 to about100 and generally is an integer of from 1 to about 50. Advantageously,it is found that wherein n is an integer of from about 4 to about 20,the length of such an aliphatic chain is sufficiently is long to renderthe colorant soluble in a phase change ink carrier while notsubstantially increasing a melting temperature of a resulting phasechange ink composition where the colorant is present in a largeconcentration.

Referring still to compounds of formula 3, such comprise a pair ofhalogen atoms X and Y which are bonded to the aromatic hexagonal ring ineither ortho or meta positions relative to the nitrogen atom. Thesymbolism utilized in showing the structure of compounds in accordancewith formula 3, depicts bonds from atoms X and Y extending into thecircular ring in the center of the aromatic hexagonal ring. Suchextension of bonds from X and Y into the circular ring is utilized toindicate that atoms X and Y can be bonded either meta or ortho relativeto the nitrogen bond position.

Atoms X and Y can be the same or different than one another, and can beany of the halogen atoms F, Cl, Br or I. In some advantageousembodiments, at least one of X and Y is bromine. In some advantageousembodiments, both of X and Y are bromine and such compounds can berepresented, as shown below, by formula 4.

Further, if both of the bromine atoms are bonded to the aromatichexagonal ring in ortho positions relative to the nitrogen atom,compounds of formula 4 will have the structure shown below as formula 5.

Compounds in accordance with formula 5 have a magenta color essentiallyidentical to that of C.I. Solvent Red 172. C.I. Solvent Red 172(compound 1) is not encompassed by formula 5, as the R group ofcompounds that are encompassed by formula 5 comprise a carbon chain thatis longer than 5 the methyl group of compound 1.

While C.I. Solvent Red 172 has previously been utilized in theformulation of phase change inks, its solubility or usable concentrationis limited in such formulations. Further, phase change ink formulationscontaining Solvent Red 172 suffer from a tendency for the magenta dye tocrystallize when formed lo as a solid ink of a printed image. Thistendency is exacerbated by fingerprint oils and is seen as a changewithin the printed image from a bright magenta color to dull purpleblotches.

In some particular embodiments of the present invention, it isrecognized that it is desirable to create compounds with aliphaticchains that improve the compatibility of the dye with ink base materialsas well as reducing the melting point. In addition, such improvementsreduce the tendency of the dye to crystallize when formed as a printedimage. Also, it will be recognized that substitution of halogen atomsother than bromine for atoms X and Y of compounds in accordance withformulas 3-5 will likely result in compounds having colors other thanmagenta. Additionally, it is recognized that compounds similar to thoseof formula 5, but lacking at least one of the atoms X and Y, will alsohave different colors. Such compounds are shown below as compounds inaccordance with formulas 6 and 7.

In such compounds, the group R is the same as the group R discussed forcompounds of formula 3. For formula 6, X is a halogen atom which can bepositioned in the aromatic hexagonal ring either ortho or meta relativeto the nitrogen atom. Compounds in accordance with formula 7 generallyhave a bluish-violet color.

A method of making a colorant of the present invention is described withreference to the FIG.. An aniline derivative 10, with an appropriate Rgroup, is combined with an anthraquinone derivative 15, resulting in therelease of water and formation of a compound 20, in accordance withformula 7. Compound 20 is then subjected to bromination to form compound30, which is in accordance with formula 5. As will be recognized bypersons of ordinary skill in the art, the reaction sequence described inthe FIG. can be modified to make any compound in accordance withformulas 2-7. Each of such compounds having an appropriate R groupderived from the aniline derivative 10. For example, useful compounds inaccordance with formulas 2-7 have been made where R is butyl, hexyl,dodecyl and tetradecyl.

The reactions utilized in the scheme of the FIG. are applications ofwell understood reaction chemistries. Such reaction chemistries beingdescribed in, for example, Chapter 4 of “The Chemistry and Applicationof Dyes”, which is edited by David R. Waring, and Geoffrey Hallas, andpublished by Plenum Press (1990) of New York, NY. Thus while a varietyof analogs of C.I. Solvent Red 172 have been prepared, it will beunderstood that an exemplary Is preparation of the n-butyl analog ofC.I. Solvent Red 172, is sufficient to illustrate the synthetic schemeof the FIG.. Such an exemplary preparation is presented in Examples 1and 2, below.

EXAMPLE 1 SYNTHESIS OF C.I. SOLVENT VIOLET 13, n-BUTYL ANALOG

To a 500 mL 3-necked round-bottom flask with reflux condenser, stiffingand thermometer, 10.5 g of quinizarin¹, 6.5 g of leucoquinizarin², about4 g of boric acid, 10.5 g of 4-butylaniline ³ and about 200 mL ofisopropyl alcohol were added. Stirring was initiated and the reactionheated to reflux temperature and maintained at reflux for about 20 hr.While the stirring was continued, the reaction mixture was allowed tocool to room temperature where upon about 200 mL of water was added withcontinued stirring. After about 30 min, a solid was recovered byfiltration. The recovered solid was washed with copious amounts of waterand subsequently triturated in 5% NaOH, filtered and the solids washedwith water until the filtrate was colorless.

¹ Quinizarin—available from Aceto Corporation of Lake Success, N.Y.

² Leucoquinizarin—available from Aldrich Chemicals of Milwaukee, Wis.

³4-Butylaniline—available from Aldrich Chemicals of Milwaukee, Wis.

EXAMPLE 2 SYNTHESIS OF C.I. SOLVENT RED 172, n-BUTYL ANALOG (BROMINATIONOF C.I. SOLVENT VIOLET 13, n-BUTYL ANALOG)

To a 1 L 3-necked round-bottom flask with reflux condenser, stirring,thermometer and constant pressure addition-funnel, about 50 g of thepurified product of Example 1, and 500 g of glacial acetic acid⁴ wereadded. Stirring was started and the reaction mixture heated to 50° C.Once the reaction mixture reached 50° C., drop-wise addition of 43.1 gof bromine⁵ was started. The addition rate of the bromine was adjustedas needed to maintain the temperature of the reaction mixture at 50° C.The reaction mixture was heated with stirring for an additional 6 hoursand then cooled to room temperature. A solid product was collected byfiltration and recrystallized from first glacial acetic acid and then50/50 toluene/acetic acid until pure.

⁴ Glacial Acetic Acid—available from Aldrich Chemicals of Milwaukee,Wis.

⁵ Bromine—available from Aldrich Chemicals of Milwaukee, Wis.

It will be realized that the synthesis of a colorant, in accordance withembodiments of the present invention, presented in Examples 1 and 2 isfor illustrative purposes. Thus any other colorant encompassed byformulas 2-7 as can be made by the illustrative synthetic process or anyother known synthetic process is within the scope and spirit of thepresent invention. For example, where 4-n-dodecyl-aniline is substitutedfor the 4-n-butyl aniline of Example 1, the n-dodecyl analog of C.I.Solvent Violet 13 is obtained and such is a colorant encompassed byformulas 2-7. Methods for forming other halogenated C.I. Solvent Violet13 analogs are known. Thus colorants formed by these alternate methodswill also be realized to be within the scope and spirit of the presentinvention.

Once synthesized, the colorant compounds in accordance with the presentinvention, described above with reference to formulas 2-7, areincorporated into phase change inks. Specifically, such colorantcompositions are combined with phase change ink carrier compositions toform such phase change inks. The phase change inks are advantageouslyformed such that the inks are solid at room temperature, and morespecifically are solid at temperatures below about 30° C. Further, suchphase change inks are advantageously formulated to melt at a temperatureabove 30° C. (typically much higher than 30° C.) so that the inks can bejetted through a printhead and onto a substrate. For example, anexemplary operating temperature of a printhead utilizing a phase changeink is about 140° C. Accordingly, it is advantageous to have a phasechange ink composition that has a melting temperature of at or below140° C. However, it will be realized that other phase transitiontemperatures may be advantageous and that any such other range is withinthe scope and spirit of the present invention, For example, where aprinthead has an exemplary operating temperature of 160° C., an inkcomposition having a melting temperature at or below 160° C. isadvantageously encompassed by embodiments of the present invention.Example 3 is illustrative of one such advantageous formulation.

EXAMPLE 3 MAGENTA INK FORMULATION

To a stainless steel beaker, 4265 g of Kemamide S180⁶, 940.8 g of KE100⁷, 2645.7 g of tetraamide⁸, 305 g of Santicizer 278⁹ and 16.0 g ofantioxidant N-445¹⁰ were added. The beaker was placed in an ovenmaintained temperature of about 135° C. and the materials were melted.The beaker transferred to a temperature controlled mantel, alsomaintained at a temperature of about 135° C., and blended by stirringfor approximately 30 min. To the blended mixture, 40.0 g of DDBSA¹¹,67.2 g of the purified product of Example 2 and 16.0 g of C.I. SolventRed 49¹² were added and the mixture was stirred for an additional 2 hr.The mixture was filtered hot using a Mott¹³ apparatus with a Whatman #3filter at a pressure of about 5 psi of nitrogen. The filtered phasechange ink was poured into molds and allowed to solidify into inksticks. The viscosity of the final ink product was measured using a CSRviscometer at about 140° C. and found to be about 12.9 cPs. In on, theink sticks were used as an ink source for a Tektronix Phaser Model 340printer. The ink was found to transfer completely and provide images ofgood color, print quality and durability.

⁶ Kemamide S180 —Stearyl Stearamide available from Witco of Memphis,Tenn.

⁷ KE 100 Glycerol ester of hydrogenated abietic (rosin) acid availablefrom Arakawa Chemical Industries, Ltd. of Osaka, Japan

⁸ Tetraamide—Unirez 2970 —available from Union Camp Corp. of Wayne, N.J.

⁹ Santicizer 278 —plasticizer available from Monsanto Chemical Co. ofSt. Louis, Mo.

¹⁰ Naugard 445 —antioxidant available from Uniroyal Chemical Co., Inc.of Middlebury, Conn.

¹¹ DDBSA—Bio-Soft S100 (Dodecylbenzene sulfonic acid)

¹² Sr 49—Neptune Red Base NB 543 LD—Dye available from BASF Co.,Renssalar, N.Y.

¹³ Mott Corporation, Farmington,

Phase change inks encompassed by the present invention are utilized inprinting applications by melting at least a portion of a solid ink blockto transform such portion to a liquid phase. The liquid phase ink isjetted through a printhead and applied onto a substrate. Once on thesubstrate, the ink cools to form an ink pattern which defines at least aportion of a visible image on the substrate.

It will be realized that embodiments in accordance with the presentinvention encompass any of the alternate phase change ink compositionsas can be formulated employing the exemplary method of Example 3. Thussuch alternate phase change ink compositions where alternatenon-colorant materials are combined with at least one colorantencompassed by formulas 2-7 are within the scope and spirit of theinstant invention as changing such non-colorant materials is recognizedas a design choice. In addition, such alternate phase change inkcompositions encompassing at least one colorant encompassed by formulas2-7 and employing one or more colorant materials other than theexemplary C.I. Solvent Red 49, are also recognized as being within thescope and spirit of the instant invention as such alternate colorantsare further recognized as design choices.

In compliance with the statute, the invention has been described inlanguage more or less specific as to structural and methodical features.It is to be understood, however, that the invention is not limited tothe specific features shown and described, since the means hereindisclosed comprise preferred forms of putting the invention into effect.The invention is, therefore, claimed in any of its forms ormodifications within the proper scope of the appended claimsappropriately interpreted in accordance with the doctrine ofequivalents.

What is claimed is:
 1. A phase change ink comprising a compound havingthe formula:

wherein R comprises (CH₂)_(n)CH₃, and wherein n is an integer of from 2to 50, and wherein the compound is a colorant, the ink being configuredto be a solid at temperatures below about 30° C. and to melt at atemperature above 30° C.
 2. A phase change ink comprising a compoundhaving the formula:

wherein the compound is a colorant, wherein at least one of Q₁, Q₂, Q₃and Q₄ is a halogen atom and any of Q₁, Q₂, Q₃ and Q₄ which is not ahalogen atom is a hydrogen atom; and wherein R comprises at least twocarbon atoms.
 3. The phase change ink of claim 2 wherein the halogenatom is bromine.
 4. The phase change ink of claim 2 wherein R comprisesfrom 2 to 50 carbon atoms.
 5. The phase change ink of claim 2 wherein Rcomprises (CH₂)_(n)CH₃, and wherein n is an integer of from 1 to
 50. 6.The phase change ink of claim 2 wherein R comprises (CH₂)_(n)CH₃, andwherein n is
 3. 7. A phase change ink comprising a compound having theformula:

wherein X and Y are halogen atoms and can be the same or different fromone another, and wherein R comprises at least two carbon atoms andwherein the compound is a colorant.
 8. The phase change ink of claim 7wherein at least one of the halogen atoms is bromine.
 9. The phasechange ink of claim 7 wherein both of the halogen atoms are bromine. 10.The phase change ink of claim 7 wherein R comprises from 2 to 50 carbonatoms.
 11. The phase change ink of claim 7 wherein R comprises(CH₂)_(n)CH₃, and wherein n is an integer of from 1 to
 50. 12. The phasechange ink of claim 7 wherein R comprises (CH₂)_(n)CH₃, and wherein n is3.
 13. The phase change ink of claim 7 wherein the colorant has theformula:

wherein R comprises (CH₂)_(n)CH₃, where n is an integer of from 1 to 50.14. A phase change ink comprising a colorant having the formula:

wherein R comprises at least two carbon atoms; X and Y are halogen atomsand can be the same or different from one another, and the phase changeink being configured to be a solid at temperatures below about 30° C.and to melt at a temperature above 300° C.
 15. The phase change ink ofclaim 14 wherein R comprises from 2 to 50 carbon atoms.
 16. The phasechange ink of claim 14 wherein R comprises 4 carbon atoms.
 17. The phasechange ink of claim 14 wherein R comprises (CH₂)_(n)CH₃, and wherein nis an integer of from 1 to
 100. 18. The phase change ink of claim 14wherein R comprises (CH₂)_(n)CH₃, and wherein n is 3, 5, 11 or 13.